CA2025508C - Sheet of polyvinyl butyral and polyurethane - Google Patents
Sheet of polyvinyl butyral and polyurethaneInfo
- Publication number
- CA2025508C CA2025508C CA002025508A CA2025508A CA2025508C CA 2025508 C CA2025508 C CA 2025508C CA 002025508 A CA002025508 A CA 002025508A CA 2025508 A CA2025508 A CA 2025508A CA 2025508 C CA2025508 C CA 2025508C
- Authority
- CA
- Canada
- Prior art keywords
- sheet
- polyurethane
- pvb
- diisocyanate
- polyether polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Building Environments (AREA)
Abstract
A sheet formed of a polyblend comprising, on a weight basis, a) 30 to 90% polyvinyl butyral containing about 11 to 30 % hydroxyl groups and b) 70 to 10% thermoplastic polyurethane which is the reaction product of:
i) polyether polyol or a mixture of polyether polyol and polyester polyol; and ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
the combined percentages of a) plus b) in the polyblend always equaling 100%; such sheet at 0.76mm thickness having no greater than 2% haze.
i) polyether polyol or a mixture of polyether polyol and polyester polyol; and ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
the combined percentages of a) plus b) in the polyblend always equaling 100%; such sheet at 0.76mm thickness having no greater than 2% haze.
Description
2~2~8 -1- 06-12 ( 9879 ) A
SHEET OF POLYVINYL BUTYRAL AND POLYURETEIANE
BACKGROUND OF ThF INVENTION
This invention relates to interlayer sheet for safety glass assemblies and more particularly to such sheet formed of polyblends of polyvinyl butyral and polyurethane.
Polyvinyl butyral (PVB) sheet is widely used as a clear, transparent, shock-absorbing interlayer in laminated safety glazings for motor vehicle, aircraft, architectural, security (e.g. cashier booths, prison windows, jewelry display cases etc.) and like applica-tions. For example, an automotive wi ~Chl eld contain-ing such interlayer laminated between glass sheets can absorb a blow from an occupant's head without shat-tering and in doing so dissipates significant impact energy as the windshield undergoes essentially plastic deformation.
When used as interlayer, significant plas-ticizer is usually present in the PVB and this can limit the service application or, alternatively, dictate the choice of plasticizer when the PVB is adhered to a non-glass surface in a multi-layer laminate. Such special plasticizers, however, usually detract from other desirable laminate proper-ties.
Moreover, it is further known that the optimum level of adhesion of plasticized PVB inter-layer to glass (via reaction of re~idual hydroxyl groups with SioH groups on the glass surface) occurs at nominal temperatures of about 15-21~C and this is why it is preferred in safety glazings. However, glass adhesion (and therefore the energy-absorbing properties of the laminate) appreciably deteriorates on either side of this temperature range e.g., at 0~F
(-17.7~C) and 120~F (49~C).
Furthermore, as designers provide additional 2~'~'?.~J~
-2- 06-12(9879)A
sophisticated performance features in safety glazings by incorporating added functional layers, it is necessary to be concerned with adherence of the PVB to such layers to preserve the desired energy-absorption properties.
SUMMARY OF THE INV~;NlION
Now improvements have been made in PVB
sheet which minimize or overcome the aforementioned deficiencies of the prior art.
Accordingly, a principal object of this invention is to provide a sheet formed of a mechani-cally and optically compatible blend of PVB with another polymer.
Another object is to provide such a sheet wherein the other polymer is selected to enh~nce properties in which PVB alone is deficient.
An additional object is to provide sheet formed of mechanically and optically compatible blends of PVB and polyurethane (PU), either with or without plasticizer, having properties which can be control-lably varied depending on the blend ratio of compon-ents.
Other objects of this invention will in part be obvious and will in part appear from the following description and claims.
These and other objects are accomplished by providing a sheet formed of a polyblend comprising, on a weight basis, a) 30 to 90% PVB cont~in-ng about 11 to 30%, preferably about 15 to 25%, hydroxyl groups and b) 70 to 10% thermoplastic polyurethane which is the reaction product of:
(i) polyether polyol or a mixture of poly-ether polyol and polyester polyol; and (ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
2~J~
SHEET OF POLYVINYL BUTYRAL AND POLYURETEIANE
BACKGROUND OF ThF INVENTION
This invention relates to interlayer sheet for safety glass assemblies and more particularly to such sheet formed of polyblends of polyvinyl butyral and polyurethane.
Polyvinyl butyral (PVB) sheet is widely used as a clear, transparent, shock-absorbing interlayer in laminated safety glazings for motor vehicle, aircraft, architectural, security (e.g. cashier booths, prison windows, jewelry display cases etc.) and like applica-tions. For example, an automotive wi ~Chl eld contain-ing such interlayer laminated between glass sheets can absorb a blow from an occupant's head without shat-tering and in doing so dissipates significant impact energy as the windshield undergoes essentially plastic deformation.
When used as interlayer, significant plas-ticizer is usually present in the PVB and this can limit the service application or, alternatively, dictate the choice of plasticizer when the PVB is adhered to a non-glass surface in a multi-layer laminate. Such special plasticizers, however, usually detract from other desirable laminate proper-ties.
Moreover, it is further known that the optimum level of adhesion of plasticized PVB inter-layer to glass (via reaction of re~idual hydroxyl groups with SioH groups on the glass surface) occurs at nominal temperatures of about 15-21~C and this is why it is preferred in safety glazings. However, glass adhesion (and therefore the energy-absorbing properties of the laminate) appreciably deteriorates on either side of this temperature range e.g., at 0~F
(-17.7~C) and 120~F (49~C).
Furthermore, as designers provide additional 2~'~'?.~J~
-2- 06-12(9879)A
sophisticated performance features in safety glazings by incorporating added functional layers, it is necessary to be concerned with adherence of the PVB to such layers to preserve the desired energy-absorption properties.
SUMMARY OF THE INV~;NlION
Now improvements have been made in PVB
sheet which minimize or overcome the aforementioned deficiencies of the prior art.
Accordingly, a principal object of this invention is to provide a sheet formed of a mechani-cally and optically compatible blend of PVB with another polymer.
Another object is to provide such a sheet wherein the other polymer is selected to enh~nce properties in which PVB alone is deficient.
An additional object is to provide sheet formed of mechanically and optically compatible blends of PVB and polyurethane (PU), either with or without plasticizer, having properties which can be control-lably varied depending on the blend ratio of compon-ents.
Other objects of this invention will in part be obvious and will in part appear from the following description and claims.
These and other objects are accomplished by providing a sheet formed of a polyblend comprising, on a weight basis, a) 30 to 90% PVB cont~in-ng about 11 to 30%, preferably about 15 to 25%, hydroxyl groups and b) 70 to 10% thermoplastic polyurethane which is the reaction product of:
(i) polyether polyol or a mixture of poly-ether polyol and polyester polyol; and (ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
2~J~
-3- 06-12(9879)A
the combined percentages of (a) plus (b) in the polyblend always egualing 100%, such sheet at 30 mils (0.76mm) thickness havin~ no greater than 2%
haze. The sheet may optionally contain plasticizer and the preferred polyurethane is prepared from cycloaliphatic diisocyanate and polyether polyol.
The preferred component ranges in the polyblend of the sheet are 30 to 70% PVB and 70 to 30% PU, with 60/40 PVB/PU most preferable.
DETAILED DESCRIPTION OF ln~ INVENTION
The PVB component of the polyblends used to form sheet of the invention has a Staudinger molecular weight of about 50,000 to 600,000, preferably 55,000 to 170,000 and constitutes on a weight basis about 11 to 30% hydroxyl groups, calculated as polyvinyl alcohol, 0 to 5% ester groups, calculated as polyvinyl ester, e.g. 0 to 2.5% acetate groups, calculated as polyvinyl acetate, with the balance being butyral groups. Preferred PVB resins contain on a weight basis, about 15 to 25% (e.g. 18-25%) of such hydroxyl groups.
PVB resin is produced by known aqueous or solvent acetalization processes wherein polyvinyl alcohol is reacted with butyraldehyde in the presence of an acid catalyst to produce PVB, followed by neutralization of the catalyst, separation, stabili-zation and drying of the PVB resin.
For optical and mechanical compatibility with PVB the PU component of the polyblends must be a preformed thermoplastic polyurethane (TPU) which is uncrosslinked. Reactive cross-linkable polyurethanes are not usable because of the chemical reaction which will occur with hydroxyls of the PVB component.
Functional TPU's contain hard and soft segments formed respectively of polymerized diisocyanate and polyol components. The ratio or weight% of hard to soft 2 ~
the combined percentages of (a) plus (b) in the polyblend always egualing 100%, such sheet at 30 mils (0.76mm) thickness havin~ no greater than 2%
haze. The sheet may optionally contain plasticizer and the preferred polyurethane is prepared from cycloaliphatic diisocyanate and polyether polyol.
The preferred component ranges in the polyblend of the sheet are 30 to 70% PVB and 70 to 30% PU, with 60/40 PVB/PU most preferable.
DETAILED DESCRIPTION OF ln~ INVENTION
The PVB component of the polyblends used to form sheet of the invention has a Staudinger molecular weight of about 50,000 to 600,000, preferably 55,000 to 170,000 and constitutes on a weight basis about 11 to 30% hydroxyl groups, calculated as polyvinyl alcohol, 0 to 5% ester groups, calculated as polyvinyl ester, e.g. 0 to 2.5% acetate groups, calculated as polyvinyl acetate, with the balance being butyral groups. Preferred PVB resins contain on a weight basis, about 15 to 25% (e.g. 18-25%) of such hydroxyl groups.
PVB resin is produced by known aqueous or solvent acetalization processes wherein polyvinyl alcohol is reacted with butyraldehyde in the presence of an acid catalyst to produce PVB, followed by neutralization of the catalyst, separation, stabili-zation and drying of the PVB resin.
For optical and mechanical compatibility with PVB the PU component of the polyblends must be a preformed thermoplastic polyurethane (TPU) which is uncrosslinked. Reactive cross-linkable polyurethanes are not usable because of the chemical reaction which will occur with hydroxyls of the PVB component.
Functional TPU's contain hard and soft segments formed respectively of polymerized diisocyanate and polyol components. The ratio or weight% of hard to soft 2 ~
-4- 06-12(9879)A
segments determines the physical properties of the TPU. In synthesizing TPU a difunctional chain ex-tender such as a diol or diamine is used to space diisocyanate molecules in the polymer ChAi n~ . A
prepolymer of diisocyanate and difunctional chain extender is preferably first prepared to avoid tox-icity problems associated with handling monomeric isocyanate.
The diisocyanate can be saturated aliphatic, either linear or cycloaliphatic (including mixtures of same) or aromatic (including mixtures of same) or mixtures of aliphatic and aromatic diisocyanates, provided always that sheet formed from blends con-tA;ning TPU's made from such various diisocyantes at 30 mils (0.76mm) thickness must have no greater than 2% haze, as hereinafter further described. Cyclo-aliphatic diisocyanates are preferred and comprise cyclohexyl diisocyanate having one or two cyclohexyl ring groups. Methylene bis (4-cyclohexyl) diisocyanate is most preferred.
The polyol component is a polyether polyol or a mixture or polyether polyol(s) and polyester polyol(s), such as linear long chain polyether or polyester diols, the molecular weight of which deter-mines the hardness of the TPU and its compatibility with PVB in the polyblend. By selectively choosing polyol molecular weight and blending the TPU obtained with PVB, it is possible to obtain a family of mechan-ically and optically compatible polymers which can be used to form sheet having properties tailored for specific applications. Preferred polyols are poly-ether polyols such as polytetraalkylene ether glycols where alkylene is Cl-C4. For optimum compatibility in the polyblend, polytetralkylene ether glycol molecular weight should be between about 90 to 4000, preferably 650 to 3000.
A plasticizer (or blend of plasticizers) 2~ r~
segments determines the physical properties of the TPU. In synthesizing TPU a difunctional chain ex-tender such as a diol or diamine is used to space diisocyanate molecules in the polymer ChAi n~ . A
prepolymer of diisocyanate and difunctional chain extender is preferably first prepared to avoid tox-icity problems associated with handling monomeric isocyanate.
The diisocyanate can be saturated aliphatic, either linear or cycloaliphatic (including mixtures of same) or aromatic (including mixtures of same) or mixtures of aliphatic and aromatic diisocyanates, provided always that sheet formed from blends con-tA;ning TPU's made from such various diisocyantes at 30 mils (0.76mm) thickness must have no greater than 2% haze, as hereinafter further described. Cyclo-aliphatic diisocyanates are preferred and comprise cyclohexyl diisocyanate having one or two cyclohexyl ring groups. Methylene bis (4-cyclohexyl) diisocyanate is most preferred.
The polyol component is a polyether polyol or a mixture or polyether polyol(s) and polyester polyol(s), such as linear long chain polyether or polyester diols, the molecular weight of which deter-mines the hardness of the TPU and its compatibility with PVB in the polyblend. By selectively choosing polyol molecular weight and blending the TPU obtained with PVB, it is possible to obtain a family of mechan-ically and optically compatible polymers which can be used to form sheet having properties tailored for specific applications. Preferred polyols are poly-ether polyols such as polytetraalkylene ether glycols where alkylene is Cl-C4. For optimum compatibility in the polyblend, polytetralkylene ether glycol molecular weight should be between about 90 to 4000, preferably 650 to 3000.
A plasticizer (or blend of plasticizers) 2~ r~
-5- 06-12(9879)A
capable of solvating the polyblend which is compatible with both the TPU and PVB can optionally be included, usually depending on the sheet application and the proportions of constituents present, the greater the content of rubbery TPU the less may be the need for a plasticizer to reduce melt viscosity during shaping.
Haze level in sheets formed from blends determines optical compatability, a value of not more than 2%
haze in a 30 mil (0.76 mm) thick sheet showing optical compatability. Potential pl~sticizer(s) include phthalates such as dibutyl, dihexyl, dioctyl, diun-decyl and diisodecyl phthalate, adipates such as di-hexyl and diocytl adipate, phosphates such as tri-cresyl and triphenyl phosphate and the like. Poly-tetramethylene ether glycol is particularly usefulat loadings of between about 3 to about 20 parts per 100 parts TPU/PVB polyblend.
The forming operation to prepare interlayer sheet from the blends is according to procedures known in the art. Forming includes fusing or melting~the polymeric thermoplastic polyblend by physical working at temperatures of about 150 to 210~C, followed by shaping of the melt into clear, transparent sheeting having a thickness of about 5 to 50 mils (0.13 to 1.3 mm). Shaping from the melt can be in conjunction with extrusion using a screw extruder or by compres-sion molding, mill rolling or like process. Preferred shaping systems involve extrusion of plasticized blend melt through a conventional sheeting die by forcing the molten polymer through a horizontally long, vertically narrow die opening substantially conforming in length and width to that of the sheet being formed, or by using a die roll system, i.e. by casting the molten polymer issuing from an extrusion die onto a specially prepared surface of a die roll in close proximity to the exit of such die.
Conventional techni~ues known to those ~ ~ 3 -6- 06-12(9879)A
skilled in the art can be used in association with the extrusion process to produce a rough surface on one or both sides of the extruding sheet. These involve the specification and control of one or more of the following: polymer molecular weight distribu-tion, water content of the melt, melt and die exit temperature, die exit geometry etc. Systems describ-ing such techniques are disclosed in U.S. Pat. Nos.
2,904,844,; 2,909,810; 3,994,654; 4,575,540 and published European Application No. 0185,863.
In addition to plasticizers, the interlayer sheet of this invention may contain other additives such as dyes, ultraviolet light stabilizers, adhesion control salts, antioxidants and may be treated with additives to improve laminating efficiency.
The invention is further described in the following illustrative examples which are not meant to restrict the invention. Unless otherwise indi-cated, all quantities are expressed in weight.
The following tests were used to provide the values and results listed in the Tables:
~ e - ASTM D1003-01 (Reapproved 1977) -Procedure A - using a Hazemeter, Hunter lab Model D25 from Hunter Associates Inc., Reston, VA. This measures optical compatibility of blend components Initial Tear Resistance - (MTR) ASTM D1004-66 (Reapproved 1981). This measures mechanical com-patibility of the polyblend components.
Glass Transition Temperature (Tg) - using a Differential ~canning Calorimeter. This measures thermodynamic compatibility, i.e. whether molecular mixin~ of the blend components occurs.
Mean Penetration Velocity(MPV) - glass laminates were positioned horizontally in a metal frame and, while at a constant laminate temperature, a five pound (2.27kg) spherical ball was dropped from a designated height against the center of the laminate.
~ 'J :~ 5 ~ ~
capable of solvating the polyblend which is compatible with both the TPU and PVB can optionally be included, usually depending on the sheet application and the proportions of constituents present, the greater the content of rubbery TPU the less may be the need for a plasticizer to reduce melt viscosity during shaping.
Haze level in sheets formed from blends determines optical compatability, a value of not more than 2%
haze in a 30 mil (0.76 mm) thick sheet showing optical compatability. Potential pl~sticizer(s) include phthalates such as dibutyl, dihexyl, dioctyl, diun-decyl and diisodecyl phthalate, adipates such as di-hexyl and diocytl adipate, phosphates such as tri-cresyl and triphenyl phosphate and the like. Poly-tetramethylene ether glycol is particularly usefulat loadings of between about 3 to about 20 parts per 100 parts TPU/PVB polyblend.
The forming operation to prepare interlayer sheet from the blends is according to procedures known in the art. Forming includes fusing or melting~the polymeric thermoplastic polyblend by physical working at temperatures of about 150 to 210~C, followed by shaping of the melt into clear, transparent sheeting having a thickness of about 5 to 50 mils (0.13 to 1.3 mm). Shaping from the melt can be in conjunction with extrusion using a screw extruder or by compres-sion molding, mill rolling or like process. Preferred shaping systems involve extrusion of plasticized blend melt through a conventional sheeting die by forcing the molten polymer through a horizontally long, vertically narrow die opening substantially conforming in length and width to that of the sheet being formed, or by using a die roll system, i.e. by casting the molten polymer issuing from an extrusion die onto a specially prepared surface of a die roll in close proximity to the exit of such die.
Conventional techni~ues known to those ~ ~ 3 -6- 06-12(9879)A
skilled in the art can be used in association with the extrusion process to produce a rough surface on one or both sides of the extruding sheet. These involve the specification and control of one or more of the following: polymer molecular weight distribu-tion, water content of the melt, melt and die exit temperature, die exit geometry etc. Systems describ-ing such techniques are disclosed in U.S. Pat. Nos.
2,904,844,; 2,909,810; 3,994,654; 4,575,540 and published European Application No. 0185,863.
In addition to plasticizers, the interlayer sheet of this invention may contain other additives such as dyes, ultraviolet light stabilizers, adhesion control salts, antioxidants and may be treated with additives to improve laminating efficiency.
The invention is further described in the following illustrative examples which are not meant to restrict the invention. Unless otherwise indi-cated, all quantities are expressed in weight.
The following tests were used to provide the values and results listed in the Tables:
~ e - ASTM D1003-01 (Reapproved 1977) -Procedure A - using a Hazemeter, Hunter lab Model D25 from Hunter Associates Inc., Reston, VA. This measures optical compatibility of blend components Initial Tear Resistance - (MTR) ASTM D1004-66 (Reapproved 1981). This measures mechanical com-patibility of the polyblend components.
Glass Transition Temperature (Tg) - using a Differential ~canning Calorimeter. This measures thermodynamic compatibility, i.e. whether molecular mixin~ of the blend components occurs.
Mean Penetration Velocity(MPV) - glass laminates were positioned horizontally in a metal frame and, while at a constant laminate temperature, a five pound (2.27kg) spherical ball was dropped from a designated height against the center of the laminate.
~ 'J :~ 5 ~ ~
-7- 06-12(9879)A
This was repeated at increasing ball-drop heights.
Two magnetic coils were vertically spaced from each other beneath the test laminate. After penetrating the laminate, the ball passed sequentially through magnetic fields created by the two coils and as these fields were disturbed, the top coil triggered a timer "on" switch while the bottom coil turned it off.
Knowing the distance between coils and the time to traverse the distance permits calculating the ball velocity. This residual ball velocity is related to the energy absorbed by the laminate and absorbed energy in miles per hour (mph) is equal to the Mean Penetration Velocity (MPV) of the laminate.
This identifies polyurethAnes capable of forming optically compatible polyblends with polyvinyl butyral. Optically compatible polyblends as 30 mil (0.76 mm) sheet are haze-free to the eye, i.e. are considered to have ~ 2% Haze.
The PVB had a nominal 18% residual polyvinyl alcohol, was in powder form and is available from Monsanto Company as Butvar~ resin.
PVB and PU pellets (without plasticizer) were dried in hot air to less then 1% H20 and then tumble blended. The dry blend was then charged to a Brabender intensive mixer maintained at 190~C and mixed until fluxed (i.e. as a fusion blend of an intimate admixture of the components) and then for 4 additional minutes. Mixer blades were rotating at about 70 rpm. Each blend was removed from the mixer and cooled to room temperature. Thirty mil (0.76mm) sheets were compression molded from the blends using heated ~350~F/176.7~C) platens at a pressure of 4000-5000 psi (27,560-34,450 kPa). The platens were faced with Mylar~ film to minimize sticking. Sheet samples were cooled to room temperature while in the ~ ~ ~ r~
This was repeated at increasing ball-drop heights.
Two magnetic coils were vertically spaced from each other beneath the test laminate. After penetrating the laminate, the ball passed sequentially through magnetic fields created by the two coils and as these fields were disturbed, the top coil triggered a timer "on" switch while the bottom coil turned it off.
Knowing the distance between coils and the time to traverse the distance permits calculating the ball velocity. This residual ball velocity is related to the energy absorbed by the laminate and absorbed energy in miles per hour (mph) is equal to the Mean Penetration Velocity (MPV) of the laminate.
This identifies polyurethAnes capable of forming optically compatible polyblends with polyvinyl butyral. Optically compatible polyblends as 30 mil (0.76 mm) sheet are haze-free to the eye, i.e. are considered to have ~ 2% Haze.
The PVB had a nominal 18% residual polyvinyl alcohol, was in powder form and is available from Monsanto Company as Butvar~ resin.
PVB and PU pellets (without plasticizer) were dried in hot air to less then 1% H20 and then tumble blended. The dry blend was then charged to a Brabender intensive mixer maintained at 190~C and mixed until fluxed (i.e. as a fusion blend of an intimate admixture of the components) and then for 4 additional minutes. Mixer blades were rotating at about 70 rpm. Each blend was removed from the mixer and cooled to room temperature. Thirty mil (0.76mm) sheets were compression molded from the blends using heated ~350~F/176.7~C) platens at a pressure of 4000-5000 psi (27,560-34,450 kPa). The platens were faced with Mylar~ film to minimize sticking. Sheet samples were cooled to room temperature while in the ~ ~ ~ r~
-8- 06-12(9879)A
press. Haze results were as follows:
TABLE I
~Haze ~oTPU In Blend 20 40 TPU Type Isocyanate Polyol cycloaliphatic polyetherl 1.60 1.53 aromatic polyether2 1.24 5.60 aromatic polyester3 90.7 1 TPU from Thermedics Inc. of Woburn, Mass. as Tecoflex EG-85A
2 TPU from Dow Chemical Co. as Pellathane 2103-70A
3 TPU from Dow Chemical Co. as Pellathane 2355-85ABR
The above data illustrates sheet formed from optically compatible, unplasticized polyblends of PVB and thermoplastic aliphatic PU formed from cyclo-aliphatic diisocyanate and polyether polyol. Likewise within the scope of the invention is the sheet at <2%
(i.e. 1.24%) haze formed of the polyblend con~in;ng TPU made from aromatic diisocyanate and polyether polyol at the 20% TPU level in the blend.
The above procedure was repeated using 1% and 2%
in the blend of a reactive polyurethane in the form of a liquid prepolymer obtained from Uniroyal Chemical Co. as Adiprene LW520 cont~in; ng significant unreacted isocyanate. The PVB/PU blends crosslinked in the Brabender to an infusible thermoset block which would not melt and were not considered thermoplastic. This is due to reaction between the residual hydroxyl of the PVB and the diisocyanate of the PU which does not occur using a thermoplastic PU because all hydroxy-reactive isocyanate groups are substantially fully reacted.
This shows optically, mechanically, and 2 ~J .~ v a ~ ~
press. Haze results were as follows:
TABLE I
~Haze ~oTPU In Blend 20 40 TPU Type Isocyanate Polyol cycloaliphatic polyetherl 1.60 1.53 aromatic polyether2 1.24 5.60 aromatic polyester3 90.7 1 TPU from Thermedics Inc. of Woburn, Mass. as Tecoflex EG-85A
2 TPU from Dow Chemical Co. as Pellathane 2103-70A
3 TPU from Dow Chemical Co. as Pellathane 2355-85ABR
The above data illustrates sheet formed from optically compatible, unplasticized polyblends of PVB and thermoplastic aliphatic PU formed from cyclo-aliphatic diisocyanate and polyether polyol. Likewise within the scope of the invention is the sheet at <2%
(i.e. 1.24%) haze formed of the polyblend con~in;ng TPU made from aromatic diisocyanate and polyether polyol at the 20% TPU level in the blend.
The above procedure was repeated using 1% and 2%
in the blend of a reactive polyurethane in the form of a liquid prepolymer obtained from Uniroyal Chemical Co. as Adiprene LW520 cont~in; ng significant unreacted isocyanate. The PVB/PU blends crosslinked in the Brabender to an infusible thermoset block which would not melt and were not considered thermoplastic. This is due to reaction between the residual hydroxyl of the PVB and the diisocyanate of the PU which does not occur using a thermoplastic PU because all hydroxy-reactive isocyanate groups are substantially fully reacted.
This shows optically, mechanically, and 2 ~J .~ v a ~ ~
-9- 06-12(9879)A
thermodynamically compatible polyblends at various concentrations of PVB and TPU. The TPU was the reaction product of methylene bis (cyclohexyl) di-isocyanate (HMD), poly (tetramethylene ether glycol) (PTMEG) and 1,4 butane diol (chain extender). This TPU is available from Thermedics Inc, Woburn, MA., as Tecoflex EG-85A.
The procedure of Example 1 was repeated at various blend ratios without plasticizer. Sheets prepared from the blends were no inAl 30 mil (0.76mm) thick. Results were as follows:
TABLE II
% TPU
P~operty 0* 0 10 20 40 60 ~ Haze <1 <1 l.9S 1.60 1.53 2.51 (kN/m) 52.5 280 275 220 119 82 Tg (~C) 18 73 63 59 42 22 * contA;ne~ 32phr dihexyl adipate The above data showing less than 2% haze illustrates 30 mil sheet formed from unplasticized optically compatible blends at TPU concentrations from unplasticized 10 to somewhat less than 60%. The MTR
data reflecting mechanical compatability shows that at 10-60% TPU, MTR exceeds the 52.5kN/m of the plasti-cized 100% PVB control (i.e. 0* TPU). The single Tg's reflect thermodynamic compatability of the components.
This shows compatible plasticizers at various blend ratios.
The procedure of Example 1 was repea'ed at various blend ratios using dihexyl adipate and various polytetramethylene ether glycols (PTMEG) as plasticizers at various loadings shown in Table III
as parts per hundred resin (phr) units. PTMEG is 2 ~ &
-lO- 06-12(9879)A
available as Terathane from E.I. Dupont de Nemours and Co.; molecular weight was 650 to 2000. The plasti-cizer(s) were added during dry blending where it was dispersed in and absorbed by the polymer solids.
Results were as follows:
TABLE III
Efficiency cf Plasticizers in PVB/TPU Blends PVB, X 80 60 60 60 60 60 60 60 60 60 60 Tecoflex 85A,Z 20 40 4040 40 40 40 40 40 40 40 Dihexyl adipate 15 15 Terathane 650 5 10 15 " 1000 5 10 15 " 2000 5 10 15 MTR (kN/m) 5643.889.2 63~2.568.254.2 5671.8 63 54.2 lS % Haze 1.92.3 2.6 1.5 1.5 2.1 1.6 1.4 3.3 3.~ 5.7 Tg,~C 29 28 32 30 15 34 33 29 33 34 26 In view of <2 % haze, MTR values comparable with that for conventional plasticized PVB (52.5kN/m from Ex. 2) and single Tg's, these results-illustrate sheet of plasticized PVB/TPU polyblends.
As PTMEG molecular weight decreases, plas-ticizing effectiveness increases at constant phr loadings. Therefore, as the PVB/TPU ratio in the blend is varied it may be necessary to use PTMEG's of different molecular weights and amounts to get the desired compatibility; for example, at higher PTMEG
molecular weight, more than 15 phr may be required.
This shows how glass laminate impact per-formance varies with temperature using sheet of theinvention.
14" X 14" (35.6x35.6cm) two ply glass laminates were prepared using 30 mil sheet at 60/40 2 ,' )! ~ j & ~
thermodynamically compatible polyblends at various concentrations of PVB and TPU. The TPU was the reaction product of methylene bis (cyclohexyl) di-isocyanate (HMD), poly (tetramethylene ether glycol) (PTMEG) and 1,4 butane diol (chain extender). This TPU is available from Thermedics Inc, Woburn, MA., as Tecoflex EG-85A.
The procedure of Example 1 was repeated at various blend ratios without plasticizer. Sheets prepared from the blends were no inAl 30 mil (0.76mm) thick. Results were as follows:
TABLE II
% TPU
P~operty 0* 0 10 20 40 60 ~ Haze <1 <1 l.9S 1.60 1.53 2.51 (kN/m) 52.5 280 275 220 119 82 Tg (~C) 18 73 63 59 42 22 * contA;ne~ 32phr dihexyl adipate The above data showing less than 2% haze illustrates 30 mil sheet formed from unplasticized optically compatible blends at TPU concentrations from unplasticized 10 to somewhat less than 60%. The MTR
data reflecting mechanical compatability shows that at 10-60% TPU, MTR exceeds the 52.5kN/m of the plasti-cized 100% PVB control (i.e. 0* TPU). The single Tg's reflect thermodynamic compatability of the components.
This shows compatible plasticizers at various blend ratios.
The procedure of Example 1 was repea'ed at various blend ratios using dihexyl adipate and various polytetramethylene ether glycols (PTMEG) as plasticizers at various loadings shown in Table III
as parts per hundred resin (phr) units. PTMEG is 2 ~ &
-lO- 06-12(9879)A
available as Terathane from E.I. Dupont de Nemours and Co.; molecular weight was 650 to 2000. The plasti-cizer(s) were added during dry blending where it was dispersed in and absorbed by the polymer solids.
Results were as follows:
TABLE III
Efficiency cf Plasticizers in PVB/TPU Blends PVB, X 80 60 60 60 60 60 60 60 60 60 60 Tecoflex 85A,Z 20 40 4040 40 40 40 40 40 40 40 Dihexyl adipate 15 15 Terathane 650 5 10 15 " 1000 5 10 15 " 2000 5 10 15 MTR (kN/m) 5643.889.2 63~2.568.254.2 5671.8 63 54.2 lS % Haze 1.92.3 2.6 1.5 1.5 2.1 1.6 1.4 3.3 3.~ 5.7 Tg,~C 29 28 32 30 15 34 33 29 33 34 26 In view of <2 % haze, MTR values comparable with that for conventional plasticized PVB (52.5kN/m from Ex. 2) and single Tg's, these results-illustrate sheet of plasticized PVB/TPU polyblends.
As PTMEG molecular weight decreases, plas-ticizing effectiveness increases at constant phr loadings. Therefore, as the PVB/TPU ratio in the blend is varied it may be necessary to use PTMEG's of different molecular weights and amounts to get the desired compatibility; for example, at higher PTMEG
molecular weight, more than 15 phr may be required.
This shows how glass laminate impact per-formance varies with temperature using sheet of theinvention.
14" X 14" (35.6x35.6cm) two ply glass laminates were prepared using 30 mil sheet at 60/40 2 ,' )! ~ j & ~
-11- 06-12(9879)A
PVB/TPU at 320~F ~160~C) and 225 psi (1550 kPa) laminating conditions. Saflex~ TG sheet made from the Butvar~ resin of Example 1 cont~ining 32 phr dihexyl adipate was the control. TPU was Tecoflex EG-85A;
plasticizer (7.5 phr) was Terethane 650 (polytetra-methylene ether glycol). Five laminates and controls were tested. Results (average for the five samples) were as follows:
Table IV
MPV (mph) at Temperature Laminate Interlayer 0~F(-17~C) 60~F(15.6~C) 120~F(48.4~C) Saflex TG(control) 16.8 26.0 lg.6 PVB/TPU(unplasticized) 18.6 22.3 24.9 PVB/TPU(plasticized) 21.6 22.3 22.9 The above data shows that in comparison with the plasticized PVB sheet control, impact per-formance of laminates using sheet formed from an unplasticized 60/40 blend i) at -17~C was better than the control; ii) at 15.6~C was somewhat less than the control while iii) at 48.4~C was significantly (27%) better than the control. Importantly, the addition of 7.5 phr plasticizer produced a nearly flat impact versus temperature profile vis-a-vis the control.
This means that in commercial systems safety per-formance need not be compromised at the ends of the temperature range to which in service the laminate, such as a windshield, might be exposed.
EXAMPLE V
This shows haze level of sheet from blends cont~;ning various types and concentrations of TPU's.
The procedures of Example I for preparing the blends and sheet (30 mil, 0.76 mm thick) are repeated. Haze results were as follows:
2~ 'J~--12- 06-12(9879)A
Table V
Component Trade Name TPU Type Weight Z in Blend Butvar~ PVB resin 60 60 60 60 Tecoflex EG-85A aliphatic polyether 24 32 24 32 Quinnl PN03-101 aliphatic polyester 16 8 _ _ Pellathane 2103-70A aromatic polyether _ _ 16 8 ZHaze 8.9 3.0 1.7 1.8 1 K.J. Quinn & Co. Inc., Malden, Mass.
These data show that by manipulating concen-tration and choosing TPU type blended with PVB, 30 mil (0.76mm) thick sheet having ~ 2% haze can be obtained.
The preceding description is for illustra-tion only and is not to be taken in a limited sense.
Various modifications and alterations will be readily suggested to persons skilled in the art. It is intended, therefore, that the foregoing be considered as exemplary only and that the scope of the invention be ascertained from the following claims.
PVB/TPU at 320~F ~160~C) and 225 psi (1550 kPa) laminating conditions. Saflex~ TG sheet made from the Butvar~ resin of Example 1 cont~ining 32 phr dihexyl adipate was the control. TPU was Tecoflex EG-85A;
plasticizer (7.5 phr) was Terethane 650 (polytetra-methylene ether glycol). Five laminates and controls were tested. Results (average for the five samples) were as follows:
Table IV
MPV (mph) at Temperature Laminate Interlayer 0~F(-17~C) 60~F(15.6~C) 120~F(48.4~C) Saflex TG(control) 16.8 26.0 lg.6 PVB/TPU(unplasticized) 18.6 22.3 24.9 PVB/TPU(plasticized) 21.6 22.3 22.9 The above data shows that in comparison with the plasticized PVB sheet control, impact per-formance of laminates using sheet formed from an unplasticized 60/40 blend i) at -17~C was better than the control; ii) at 15.6~C was somewhat less than the control while iii) at 48.4~C was significantly (27%) better than the control. Importantly, the addition of 7.5 phr plasticizer produced a nearly flat impact versus temperature profile vis-a-vis the control.
This means that in commercial systems safety per-formance need not be compromised at the ends of the temperature range to which in service the laminate, such as a windshield, might be exposed.
EXAMPLE V
This shows haze level of sheet from blends cont~;ning various types and concentrations of TPU's.
The procedures of Example I for preparing the blends and sheet (30 mil, 0.76 mm thick) are repeated. Haze results were as follows:
2~ 'J~--12- 06-12(9879)A
Table V
Component Trade Name TPU Type Weight Z in Blend Butvar~ PVB resin 60 60 60 60 Tecoflex EG-85A aliphatic polyether 24 32 24 32 Quinnl PN03-101 aliphatic polyester 16 8 _ _ Pellathane 2103-70A aromatic polyether _ _ 16 8 ZHaze 8.9 3.0 1.7 1.8 1 K.J. Quinn & Co. Inc., Malden, Mass.
These data show that by manipulating concen-tration and choosing TPU type blended with PVB, 30 mil (0.76mm) thick sheet having ~ 2% haze can be obtained.
The preceding description is for illustra-tion only and is not to be taken in a limited sense.
Various modifications and alterations will be readily suggested to persons skilled in the art. It is intended, therefore, that the foregoing be considered as exemplary only and that the scope of the invention be ascertained from the following claims.
Claims (14)
1. A sheet formed of a polyblend comprising, on a weight basis, a) 30 to 90% polyvinyl butyral containing 11 to 30% hydroxyl groups and b) 70 to 10%
thermoplastic polyurethane which is the reaction product of:
i) polyether polyol or a mixture of polyether polyol and polyester polyol; and ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
the combined percentages of a) plus b) in the polyblend always equaling 100%;
said sheet at 0.76mm thickness having no greater than 2% haze.
thermoplastic polyurethane which is the reaction product of:
i) polyether polyol or a mixture of polyether polyol and polyester polyol; and ii) aliphatic diisocyanate, aromatic diisocyanate or a mixture of aliphatic and aromatic diisocyanates;
the combined percentages of a) plus b) in the polyblend always equaling 100%;
said sheet at 0.76mm thickness having no greater than 2% haze.
2. The sheet of claim 1 containing plasticizer .
3. The sheet of claim 1 devoid of plasticizer.
4. The sheet of any of claims 1, 2 or 3 wherein the polyvinyl butyral contains about 15 to 25%
hydroxyl groups.
hydroxyl groups.
5. The sheet of claim 4 wherein the polyblend contains 30 to 70% polyvinyl butyral and 70 to 30% polyurethane.
6. The sheet of claim 5 wherein the polyurethane is prepared using a polyether polyol.
7. The sheet of claim 6 wherein the polyurethane is prepared from cycloalipatic diisocyanate and said polyether polyol.
8. An energy-absorbing, the thermoplastic sheet having no more than 2% haze comprising:
(a) 100 weight parts of a compatible mixture of 30 to 70 weight % polyvinyl butyral containing about 15 to 25 weight % hydroxyl groups and 70 to 30 weight percent aliphatic polyurethane; and (b) about 3 to about 20 weight parts plasticizer.
(a) 100 weight parts of a compatible mixture of 30 to 70 weight % polyvinyl butyral containing about 15 to 25 weight % hydroxyl groups and 70 to 30 weight percent aliphatic polyurethane; and (b) about 3 to about 20 weight parts plasticizer.
9. The sheet of claim 8 wherein the polyurethane is the reaction product of an aliphatic diisocyanate and polyether polyol.
10. The sheet of claim 9 wherein the diisocyanate has one or two cyclohexyl ring groups.
11. The sheet of claim 10 wherein the polyether polyol is polytetraalkylene ether glycol.
12. The sheet of any of claims 8, 9, 10 or 11 wherein the plasticizer is polytetramethylene ether glycol.
13. The sheet of claim 12 wherein the molecular weight of the polytetramethylene ether glycol is between about 90 to 4000.
14. The sheet of claim 13 wherein said molecular weight is between 650 to 3000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/408,831 US5028658A (en) | 1989-09-18 | 1989-09-18 | Sheet of polyvinyl butyral and polyurethane |
| US07/408,831 | 1989-09-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2025508A1 CA2025508A1 (en) | 1991-03-19 |
| CA2025508C true CA2025508C (en) | 1997-11-18 |
Family
ID=23617955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002025508A Expired - Fee Related CA2025508C (en) | 1989-09-18 | 1990-09-17 | Sheet of polyvinyl butyral and polyurethane |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5028658A (en) |
| EP (1) | EP0419438B1 (en) |
| JP (1) | JPH03122131A (en) |
| KR (1) | KR930006438B1 (en) |
| AT (1) | ATE126814T1 (en) |
| AU (1) | AU631924B2 (en) |
| BR (1) | BR9004619A (en) |
| CA (1) | CA2025508C (en) |
| DE (1) | DE69021812T2 (en) |
| DK (1) | DK0419438T3 (en) |
| ES (1) | ES2077667T3 (en) |
| GR (1) | GR3017927T3 (en) |
| MX (1) | MX172649B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212014A (en) * | 1991-11-08 | 1993-05-18 | Monsanto Company | Polycarbonate sheet laminated to plasticized polyvinyl butyral sheet |
| US5332774A (en) * | 1992-10-16 | 1994-07-26 | Arco Chemical Technology, L.P. | Polyvinyl acetal resins based on hydroxyaldehydes and use of the resins in laminar structures |
| NO980120L (en) * | 1997-01-13 | 1998-07-14 | Armstrong World Ind Inc | Polymer composition suitable as resilient flooring material or welding electrode |
| US6953758B2 (en) | 1998-05-12 | 2005-10-11 | Ppg Industries Ohio, Inc. | Limited visible transmission blue glasses |
| US20050238887A1 (en) * | 2004-04-27 | 2005-10-27 | D Errico John J | Infrared reflecting multiple layer glass panels |
| US20060189753A1 (en) * | 2005-02-18 | 2006-08-24 | Wagner Mark Y | Cores made from unplasticized polyvinyl butyral for wound plastic sheets |
| WO2008027046A1 (en) * | 2006-08-31 | 2008-03-06 | Kimberly-Clark Worldwide, Inc. | Highly breathable biodegradable films |
| US8227658B2 (en) | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
| US7998888B2 (en) * | 2008-03-28 | 2011-08-16 | Kimberly-Clark Worldwide, Inc. | Thermoplastic starch for use in melt-extruded substrates |
| US8147965B2 (en) | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
| US8338508B2 (en) * | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
| US8927617B2 (en) * | 2008-06-30 | 2015-01-06 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
| US8188185B2 (en) * | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
| US8759279B2 (en) * | 2008-06-30 | 2014-06-24 | Kimberly-Clark Worldwide, Inc. | Fragranced biodegradable film |
| US8283006B2 (en) * | 2008-12-18 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Injection molding material containing starch and plant protein |
| US8329601B2 (en) | 2008-12-18 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable and renewable film |
| TW201113610A (en) * | 2009-10-12 | 2011-04-16 | Chunghwa Picture Tubes Ltd | Method of forming a flexible display panel and alignment layer and spacer thereof |
| US11248097B2 (en) | 2013-02-05 | 2022-02-15 | 3M Innovative Properties Company | Graphic article |
| EP3156222A1 (en) | 2015-10-16 | 2017-04-19 | Tarkett GDL | Decorative multi-layer surface covering comprising polyvinyl butyral |
| EP3156223A1 (en) | 2015-10-16 | 2017-04-19 | Tarkett GDL | Decorative multi-layer surface covering comprising polyvinyl butyral |
| WO2017064260A1 (en) | 2015-10-16 | 2017-04-20 | Tarkett Gdl | Decorative multi-layer surface covering comprising polyvinyl butyral |
| WO2018083280A1 (en) | 2016-11-07 | 2018-05-11 | Kuraray Europe Gmbh | Fabrication process for laminated glass comprising a functional film |
| US20220081561A1 (en) * | 2019-01-09 | 2022-03-17 | Avient Corporation | Thermoplastic polyurethane compounds exhibiting enhanced stain resistance |
| US11697733B2 (en) | 2019-01-09 | 2023-07-11 | Avient Corporation | Thermoplastic polyurethane compounds exhibiting stain resistance and enhanced UV stability |
| WO2023028216A1 (en) * | 2021-08-27 | 2023-03-02 | Eastman Chemical Company | Thermoplastic polyurethane compositions comprising aliphatic thermoplastic polyurethanes that are useful as auto wraps |
| CN117940475A (en) * | 2021-08-27 | 2024-04-26 | 伊士曼化工公司 | Films comprising aliphatic thermoplastic polyurethane and polyvinyl acetal useful as automotive films |
| WO2023028202A1 (en) * | 2021-08-27 | 2023-03-02 | Eastman Chemical Company | Films comprising polyurethanes and plasticized polyvinlyl acetals that are useful as auto wraps |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA834106A (en) * | 1970-02-10 | M. Craven James | Microporous polymeric materials coated with polyurethanes | |
| IT699711A (en) * | 1962-07-11 | |||
| US3458388A (en) * | 1967-08-01 | 1969-07-29 | Du Pont | Glass-polyurethane-polyvinylbutyral-polyurethane-glass laminate |
| US3620905A (en) * | 1969-10-21 | 1971-11-16 | Du Pont | Optically clear thermoplastic polyurethanes |
| US3671370A (en) * | 1970-06-15 | 1972-06-20 | Ppg Industries Inc | Integral transparent safety glass armor unit |
| DE2228299C3 (en) * | 1972-06-09 | 1985-11-14 | Saint-Gobain Industries, Neuilly-sur-Seine | Safety glass pane |
| FR2251608B1 (en) * | 1973-11-16 | 1977-09-23 | Saint Gobain | |
| JPS57199650A (en) * | 1981-06-03 | 1982-12-07 | Asahi Glass Co Ltd | Polyurethane sheet for laminating and glass-polyurethane laminate |
| JPS58213660A (en) * | 1982-06-08 | 1983-12-12 | Asahi Glass Co Ltd | Preparation of laminated safety glass |
| GB2134445A (en) * | 1983-02-01 | 1984-08-15 | Pilkington Brothers Plc | Laminated glazing unit |
| JPS59226063A (en) * | 1983-06-03 | 1984-12-19 | Asahi Pen:Kk | Aerosol paint stock solution composition forming flexible coating film |
| JPH064786B2 (en) * | 1985-04-17 | 1994-01-19 | 関西ペイント株式会社 | Magnetic coating composition |
| JPS61274936A (en) * | 1985-05-31 | 1986-12-05 | 住友ベークライト株式会社 | Heat-resistant composite film |
| US4937147A (en) * | 1989-04-10 | 1990-06-26 | Monsanto Company | Transparent polymeric laminate |
-
1989
- 1989-09-18 US US07/408,831 patent/US5028658A/en not_active Expired - Lifetime
-
1990
- 1990-09-17 EP EP90870149A patent/EP0419438B1/en not_active Expired - Lifetime
- 1990-09-17 DE DE69021812T patent/DE69021812T2/en not_active Expired - Fee Related
- 1990-09-17 DK DK90870149.3T patent/DK0419438T3/en active
- 1990-09-17 JP JP2246943A patent/JPH03122131A/en active Pending
- 1990-09-17 CA CA002025508A patent/CA2025508C/en not_active Expired - Fee Related
- 1990-09-17 MX MX022420A patent/MX172649B/en unknown
- 1990-09-17 BR BR909004619A patent/BR9004619A/en not_active IP Right Cessation
- 1990-09-17 ES ES90870149T patent/ES2077667T3/en not_active Expired - Lifetime
- 1990-09-17 KR KR1019900014679A patent/KR930006438B1/en not_active IP Right Cessation
- 1990-09-17 AT AT90870149T patent/ATE126814T1/en not_active IP Right Cessation
- 1990-09-17 AU AU62571/90A patent/AU631924B2/en not_active Ceased
-
1995
- 1995-10-31 GR GR950403033T patent/GR3017927T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE69021812D1 (en) | 1995-09-28 |
| EP0419438A1 (en) | 1991-03-27 |
| ATE126814T1 (en) | 1995-09-15 |
| ES2077667T3 (en) | 1995-12-01 |
| AU631924B2 (en) | 1992-12-10 |
| DE69021812T2 (en) | 1996-03-21 |
| US5028658A (en) | 1991-07-02 |
| BR9004619A (en) | 1991-09-10 |
| GR3017927T3 (en) | 1996-01-31 |
| CA2025508A1 (en) | 1991-03-19 |
| KR910006402A (en) | 1991-04-29 |
| AU6257190A (en) | 1991-03-21 |
| KR930006438B1 (en) | 1993-07-16 |
| EP0419438B1 (en) | 1995-08-23 |
| MX172649B (en) | 1994-01-05 |
| DK0419438T3 (en) | 1995-12-27 |
| JPH03122131A (en) | 1991-05-24 |
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